JPH06502402A - Method for producing a concentrated aqueous dispersion of α-sulfo fatty acid monosalt and/or disalt - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Process for producing a concentrated aqueous dispersion of α-sulfofatty acid salts and/or two groups The present invention provides , by sulfonation of saturated fatty acids and/or fatty acid mixtures with sulfur dioxide. A method for producing a concentrated dispersion of α-sulfo fatty acid salts and/or two groups, comprising: Dispersion by adding anionic and/or nonionic surfactants during the neutralization step The present invention relates to a manufacturing method for improving the fluidity of the product. The present invention also provides this method. It also relates to the concentrated dispersion of the α-sulfo fatty acid salt and/or two groups thus obtained. Ru.

α-Sulfo fatty acid di-salt (hereinafter abbreviated as di-group) by sulfonation of fatty acid The manufacture is known per se from the literature. For example, according to US Pat. No. 1,926,442, Then, saturated carboxylic acids are reacted with strong sulfonating agents under aggressive reaction conditions. It is made into α-sulfo fatty acid disalt. As suitable sulfonating reagents, two Oxidized sulfur, oleum and chlorosulfonic acid are mentioned. Sulfonation reaction If the acidic sulfonation product obtained in the α- A sulfo fatty acid salt (hereinafter abbreviated as monosalt) is obtained.

Furthermore, the C+6-U fatty acid series is known to be characterized by good detergent properties. There is. In particular, the applicant's European Patent No. 112291 and European Patent No. 112292 reference.

Monosalts can be used in detergents, e.g. by direct neutralization or when used in detergent formulations. Because it can be easily converted into two groups indirectly by the alkali in the slurry, - salt is also a detergent. It is an extremely important surfactant.

In fact, in subsequent applications, anionic surfactants are often used as thick fluids. It is used in the form of an aqueous paste. Therefore, a thick liquid monosalt and /or two pastes are required. However, until now, industrial sulfonate of saturated fatty acids monosalt and/or dibasic water obtained after partial or complete neutralization in At concentrations of 20 to 30% by weight or more, the viscosity of the paste becomes extremely high and it is no longer possible to pump it. Since it was not possible to use a thick and fluid mono- and/or double-base paste, was not easily obtained.

Monosalt and/or increased content of monosalt and/or digroup in the paste Between the increased viscosity of the two aqueous pastes and the low water solubility of these surfactants, is relevant. Data from the literature are summarized in Tables 1 and 2.

Potassium 0.04 0.49 1 Ginny (R, G, B15tline Jr.), Ginny Starton (A, J, 5tirton): Journal of American Oil Chemistry Ta Society (JAm, ○il Chew, Soc,) 1957 ( 34) 100 References 2 J.K. Weil, Ni. ・J.A. Stirton (A.

J, 5tirton); E. W. Maure r), D.O. Old (W, C, Au1t), D.O. Palm (W, E, Pa1m); Journal of American Oil Chemistry Society, 1958 Reference 3 N.J. Stirton (A, J, 5 tirton): J.K. Weil: Surfer S erfactant Science Series (Sci.

Ser, ), Volume 2, Part 2: “Anionic Surfactants (Anio nic　5urfactants)'', page 388, Marcel Detska (M arcel Dekker) 1976　With conventional technology, thick fluid The problem of an industrially useful method for producing aqueous dispersions of mono- and/or di-salts has been fully addressed. It wasn't resolved in a minute.

Therefore, the problem to be solved by the present invention is to use sulfur dioxide gas from saturated fatty acids. Production of thick, fluid mono- and/or di-salt dispersions by sulfonation The objective is to provide a commercial manufacturing method.

The present invention shows that when the anhydrous bicyclic powder is introduced into water, a thick fluid paste is formed. This is based on the observation that However, for the production of anhydrous bicyclic powder, at least one other process step, such as crystallization, evaporative dehydration, centrifugation or filtration Physical separation steps such as

But finally - a salt and/or an aqueous base to form a di-aqueous dispersion. A surfactant (A) is added during the neutralization step to improve the fluidity of the dispersion. α- by sulfonation of fatty acids and/or fatty acid mixtures with sulfur trioxide A method for producing concentrated dispersions of sulfo fatty acid salts and/or dibases has been discovered.

In particular, the method according to the invention provides that - the salt and/or digroup content is between 30 and 70% by weight; , in particular from 40 to 60% by weight, of mono- and/or di-salt aqueous dispersions. be able to.

The surfactant (A) is a liquid or fluid aqueous solution at a temperature of 60 to 90°C. It exists in the form of a paste or has at least one hydrophobic property (similar to water) in its molecules. has an organic group (unsightly) and at least one hydrophilic (has an affinity for water) group It is understood to be a substance. Hydrophobic groups contain 8 to 22 carbon atoms and can be saturated or unsaturated. with saturated, straight-chain or branched alkyl or aryl or alkaryl groups; be. The hydrophilic group is a sulfonate in the form of sodium and/or potassium salts. , sulfates and carboxylates, and ethyleneoxy and propylene An oxy group is suitable. Examples of surfactants of the present invention include alkylbenzene sulfonate. nates, alkanesulfonates, α-olefin sulfonates, α-sulfofatties acid methyl ester, alkyl sulfate, alkyl ether sulfate, They are alcohol ethoxylate and alkylphenol ethoxylate.

Particularly suitable surfactants (A) are sulfonation products of oleic acid and unsaturated fats. Sulfonation products of fatty acid triglycerides and cs-+g alcohols and ethylene oxide and/or an adduct with 3 to 10 moles of propylene oxide. O Sulfonation products of leic acid are known. For example British patent 1278.421- C is oleic acid sulfonate produced by the reaction of industrial oleic acid fraction with sulfur trioxide gas. This article describes the production of NAT. Sulfonated fatty acid triglycerides were also is known. In 1834 Runge developed olive oil and castor. A sulfonated oil was obtained by treating the oil with sulfuric acid. These sulfonated oils are still It is used as an auxiliary agent, so-called turkey red oil, when dyeing textile products. [Bar Stache (H, S tache), Bar Grosman (H, Grosman)] βman), “V7-/Schmidttel (Wascha+1ttel)”, Subu S pringer-Verlag, Berlin 1 985]. Other sulfonated oils are wetting agents for textiles, handwashing pastes, etc. Used as a thickener for paints, lacquers, corrosion inhibitors or emulsifiers for mineral oils. Pu Cosmetics Chemical Specialties (Soap Co511. ChemSpec, ), 1975, page 39].

The fatty acids and fatty acid mixtures used as starting materials for the sulfonation reaction are of vegetable origin. or using fats and oils of animal origin (terrestrial or marine) or of synthetic origin. may be used (although many use CI2-111 fatty acids; however, longer or present in fatty acids with shorter chain lengths, e.g. fatty acids of vegetable and animal origin It may also contain a small amount of the type that does. Fatty acids used in sulfonation or The iodine value of the fatty acid mixture should be - salt and/or the color quality of the two groups appropriate. Therefore, it is necessary to have a vortex of 0.5. Therefore, before sulfonation, unsaturated It is necessary to subject fatty acids to a hardening process (hydrogenation). Curing is a method known per se done by.

Sulfonation of fatty acids can be carried out batchwise or continuously. suitable for the method of the invention The reactor operates on the principle of falling film. These anti An important feature of the reactor is a device of suitable design, e.g. nozzle or overflow. The raw material to be sulfonated is transported into the reactor by the The sulfur dioxide gas should be introduced either parallel or perpendicular to this. This can also be done in the other direction. Rapid and large mass exchange, large cooling area Therefore, sulfonation proceeds under mild conditions in a continuous falling film reactor. , particularly light-colored products are generally derived. This type of reactor is for example a German reactor. It is known from patent number 2138038, and a general discussion was given by Jot Falbe (J.

FalbeX), “Surfactants in Consumer Products ( S urfactants in Consumer Products)” Bringer Verlag, pp. 61 et seq. (1987) and Kirk-Othmer. (K　i　　　　-Othmer), “Encyclopedia of Chemicals ・Technology (Encyclopedia of Chemical Tec 22, pp. 1-45 (1983).

For sulfonation, sulfur trioxide is diluted with an inert gas, preferably air or nitrogen. gas mixture containing the sulfonating agent at a concentration of 1 to 8% by volume, in particular 2 to 5% by volume. Use in a compound state.

Sulfur dioxide gas is 1.1 to 1.5 mol, preferably 1° per mol of fatty acid. It is used in amounts of 2 to 1.3 mol.

The fatty acids to be sulfonated are preheated to a temperature of 70-110°C, especially 85-95°C. and introduced into the reactor at that temperature.

After sulfonation, the resulting liquid α-sulfo fatty acid is heated at 70-110°C, preferably Siege for 2 minutes at a temperature of 80-95°C for 2-30 minutes, preferably 5-15 minutes. In step 1 of the continuous sulfonation process, this process step to increase the degree of sulfonation is carried out in a sulfonation reactor. It is carried out in a heating tube after the reaction (so-called post-reaction coil). This method will help you The degree of honing can reach 80-95%.

The acidic sulfonation product obtained during the sulfonation reaction is neutralized with an aqueous base and simultaneously by adding surfactant (A) to the resulting mono- and/or di-salt dispersion stream. improve dynamics.

Suitable neutralizing bases include in particular ammonia, alkali metal and alkaline earth metal water. It is an oxide. Sodium hydroxide and potassium hydroxide or these two types Mixtures of bases are particularly suitable. The neutralizing base is particularly used in the form of an aqueous solution.

Generally, the neutralization is carried out in such a way that the pH value is maintained between 7 and 13, in particular between 7 and 10. child A dual aqueous dispersion is obtained. However, acidic sulfonation products Neutralization is carried out to partially neutralize the corresponding monosalt or monosalt/bisalt mixture. You can. In that case, neutralization is carried out at a pH value of approximately 3-7.

In one preferred embodiment of the present invention, the surfactant (A) is 10% crude sulfonic acid. 0 parts to 0.1 to 30 parts by weight, especially 10 to 25 parts by weight of active substance. Use in appropriate amounts.

In the method of the present invention, so-called acid bleaching with hydrogen peroxide is The hyposalt may be carried out before or during neutralization to the corresponding monosalt and/or di-salt. So-called alkaline bleaching with sodium diate may be carried out after the neutralization step.

Acidic and alkaline bleaching and the combination of both bleaching methods are It is known per se, for example, German Patent No. 1179931, German Patent No. 1234709 and is described in Publication No. 1443995.

The invention is illustrated by the following examples.

Example 1. Analysis method The content of washing active substances in the surfactant aqueous paste is expressed as % by weight (WAS content ) Measured by nibton titration [DG F - Method Hm 10], The content of unsulfonated components is expressed as % by weight (US content), paste oxidation, petroleum The weight was determined after extraction with ether and evaporation of the solvent.

2. Substances used 2.1. material In the presentation of the carbon chain length distribution, the measured fatty acids are shown in a condensed notation.

The number after the letter C is the number of carbon atoms in the chain. For unsaturated fatty acid residues, apo The number of strophes indicates the number of olefinic double bonds in the chain and the name of the corresponding fatty acid. The former is shown in parentheses.

a) Tallow fatty acids [Henkel KGaA, Düsseldorf Co. : Iodine value 0.5, acid value 201.7, carbon chain distribution: Cl2 = 0.1%, C15 =0°6%, C16=27.5%, C17=2.3%, Cl8=65.7%, C 20 = 1°0%, C22 = 0.1% (gas chromatography analysis) b) Industrial use Oleic acid [derived from beef tallow] (Henkel, Düsseldorf): Iodine value 93.5 , acid value 201.7, carbon chain distribution: Cl2 = 0.1%, C14 = 2°7%, C14 '(Myristolenic acid) I08%, C15=0.5%, C16=4.1%, C16 '(palmitolenic acid) I5.4%, C17=1.0%, Cl8=1.0%, 01 8' (oleic acid) = 73.3%, C18" (linoleic acid) I8.7%, C18 ``'(Riluric acid) I 1.0%, C20' (Gadolenic acid) I 1.1% (Gas chroma (Tography analysis) C) New rapeseed oil: Iodine value 120, saponification value 1901 Carbon chain distribution C14 = 1%, palmitoleic acid = 4%, Cl8 = 1%, C18' (oleic acid) = 59%, C18'' (linoleic acid) acid) 220%, C18”’(!j/Lz:za)=9%, C20=1%, C20 '(Gadolenic acid) = 2%, C22 = 1%, C22' (Ernonic acid) = 1%2.2 ．． Anionic and nonionic surfactants a) Oleic acid sulfonate: oleic acid Sulfonate is the sulfonate of industrial oleic acid (see 2, 1, b) by S03. The following was obtained by SO2 (5% by weight in nitrogen) is introduced laterally Continuous cooling jacketed falling film reactor (length 120c+i, cross section 0.6 c), oleic acid was quantitatively introduced at 550 g/h. S○3/Nitrogen The feed of the elementary mixture is based on the olefinic double bonds present in oleic acid (i.e., iodination and The molar ratio of sulfur trioxide (X) to sulfur trioxide was controlled to be 1=09. acidic anti The reaction mixture was continuously introduced into an aqueous sodium hydroxide solution to neutralize it. Then raw The product was heated at 90° C. for 120 minutes at pH 8.5. Washing actives in aqueous solution The material content was 50% by weight.

b) Sulfonated rapeseed oil: Sulfonated rapeseed oil is a new rapeseed oil (see 2, 1, c) was obtained by sulfonation with SO5 as follows. Introducing S03 from the side Continuous cooling jacketed falling film reactor (length 12 OCI & horizontal Cross section 1 cm+.

5 moles of rapeseed oil is mixed with SO, 5 moles of gas (5% by volume in air) ) at 90°C. The acidic reaction mixture is a 10% by weight sodium hydroxide solution. was introduced continuously and neutralized. The product was then heated at 95°C for 120 minutes, The solution was separated into an aqueous surfactant paste and an organic layer containing unreacted starting material. phase After separation, the organic phase fraction was dried under reduced pressure at 80°C for 2 hours and returned to the sulfonation reaction. Ta.

The DH value of the surfactant aqueous solution was adjusted to 7.8. The following data was measured.

Solid content: 230% by weight (evaporation and dehydration) WAS content = 0.223 meq/g US content = 4.61℃ amount% SQ,'-=3.4% by weight (ion chromatography) c) LS4: Industrial C I2/l 4 fatty alcohol (carbon chain distribution: Cl2=74%, C14=26 %) with 4 moles of ethylene oxide 3, sulfonation of tallow fatty acids In a pilot scale falling film reactor [manufactured by Lurgi], Liquid tallow fatty acids (see 1, 1, 8) preheated to 90°C are added to With a processing amount of 41.2 kg (150 mol) of fatty acids, sulfur dioxide gas diluted with air (5% by volume in air). 20 mol% excess of fatty acids Sol, that is, 14.4 kg (180 mol) of SO8 was introduced in 1 hour. anti The reaction was exothermic and the temperature of the crude sulfonic acid was 101°C. subsequent age In the heating process, crude sulfonic acid is passed through a tube (post-reaction coil) heated to 90°C. did. The residence time of the crude sulfonic acid in the post-reaction coil was 10 minutes. Next, coarse slurry The fonic acid was further treated in a continuous manner as described in Comparative Example 1 and Examples 1 and 2. .

Comparative example 1 The crude sulfonic acid prepared as above (see 3) was diluted with aqueous sodium hydroxide solution. It was neutralized to a pH of about 7 at a temperature of 74°C. Washing actives and unsulfonated substances in the paste After measuring the content of the sulfonated component, the degree of sulfonation (So) was calculated as follows.

[In the formula, (A) is the fat content of WAS content (wt%), according to the following calculation formula: calculate. ] (B) = US content (weight%) The following values were obtained.

WAS content +19.5% US content: 1.93% Degree of sulfonation +87.5% Increasing the concentration of aqueous base in the neutralization step to obtain a highly concentrated bibase paste Attempts to use the above method were unsuccessful. As a result of a significant increase in viscosity, the two-base paste The WAS content of was limited to only 27% at most.

Example 1 The crude sulfonic acid (3#) prepared as above was added to a 10% by weight aqueous solution of NaO Continuously neutralize H13, 2 kg/h, and at the same time 50% by weight aqueous solution of Surain. 17.5 kg/h of acid sulfonate were introduced at a temperature of up to 80°C. During the test, hydric acid The concentration of sodium chloride is continuously increased and the oleate sulfonate of crude sulfonic acid is The concentration was kept constant.

Example 2 Sulfonated rapeseed oil and LS4 were used in the neutralization step to achieve a WAS content of 50% by weight. A pumpable bibase paste was obtained as described in Example 1. These surfactants The ratio of the agent to the crude sulfonic acid was 20% by weight in all cases.

international search report Continuation of front page (72) Inventor: Polly, Wolfgang Federal Republic of Germany Dee 4000 Düsseldorf No. 13, Heupeldeinkstraasse No. 24 (72) Inventor: Boehler, Anschgar, Federal Republic of Germany, Dee 4250 Pot rope, Zuigfried Strasse No. 80

Claims (4)

[Claims] 1. For the sulfonation of saturated fatty acids and/or fatty acid mixtures with sulfur trioxide A method for producing a concentrated dispersion of α-sulfo fatty acid monosalt and/or disalt according to , a neutralization step with an aqueous base to form an aqueous dispersion of the mono- and/or di-salts. A method characterized by adding a surfactant (A) therein to improve the fluidity of the dispersion. Regarding the law. 2. The monosalt and/or disalt content in the dispersion is 30 to 70% by weight, especially 40% by weight. 2. A method according to claim 1, characterized in that a value of ~60% by weight is prepared. 3. The surfactant (A) is added in an amount of 0.1 to 30 parts by weight, especially based on 100 parts of crude sulfonic acid. Claims characterized in that it is used in an amount such that from 10 to 25 parts by weight of active substance The method according to item 1 or 2. 4. As the surfactant (A), a sulfonated product of oleic acid, an unsaturated fatty acid moiety Sulfonated products of glycerides or C8-18 alcohols and ethylene oxy Any one of claims 1 to 3, characterized in that 3 to 10 mol of the adduct is used. Method described.